System and method for using pre-equilibrium ballistic charge carrier refraction

ABSTRACT

A method and system for using a method of pre-equilibrium ballistic charge carrier refraction comprises fabricating one or more solid-state electric generators. The solid-state electric generators include one or more of a chemically energized solid-state electric generator and a thermionic solid-state electric generator. A first material having a first charge carrier effective mass is used in a solid-state junction. A second material having a second charge carrier effective mass greater than the first charge carrier effective mass is used in the solid-state junction. A charge carrier effective mass ratio between the second effective mass and the first effective mass is greater than or equal to two.

RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.12/650,841, filed Dec. 31, 2009, now U.S. Pat. No. 8,378,207, which is adivisional of U.S. patent application Ser. No. 11/762,864, filed on Jun.14, 2007, now U.S. Pat. No. 7,663,053, which claims the benefit of U.S.Provisional Patent Application No. 60/883,748, filed on Jan. 5, 2007.

FIELD

The field of the invention relates generally to energy conversionsystems and more particularly relates to a method and system for usingpre-equilibrium ballistic charge carrier refraction.

BACKGROUND

The use of solid state junctions to convert ballistic charge carriermotion directly into electricity has recently been demonstrated inseveral novel methods and approaches. As shown in cross section in FIG.1-A, in each case a charge carrier, most often an electron, is energizedon or near a conducting surface 10A by an energizer 12A, such aschemical reactions with or without using conducting catalysts, usingphotovoltaic energizing materials, or using heat combined with a thermalgradient. In each case the charge carrier ballistically moves from aconductor 10A into a semiconductor or dielectric 11A. The conductor 10Ais so thin that the electron effectively travels through itballistically, without loosing energy or colliding with another electronor atom. The result is a voltage 14A across positive terminal 17A andnegative terminal 16A. In FIG. 1-A, the dielectric junction 15A is asemiconductor junction specifically chosen to create an electricalpotential voltage barrier which tends to impede the electron ballisticmotion, shown as 11B in FIG. 1-B. FIG. 1-B shows the electricalpotential in the device as a function of distance along the device. Asshown in FIG. 2-A, electrons 21A at the conductor surface 22A have anenergy greater than the top of the potential voltage barrier. Theseelectrons 21A cross over the voltage barrier and lose energy to heat 24Abefore they settle down to the semiconductor conduction band 25A, whichseparates the charge across the conductor-dielectric junction. Electronstraveling against a potential voltage barrier convert some of theballistic electron kinetic energy into electrical potential energy 27A.The rest of the ballistic electron kinetic energy becomes heat 24A. Thevoltage 27A developed is the difference between the Fermi level of theconductor on one side 28A and the Fermi level of the dielectricconductor electrode on the other side 26A. A voltage, V (Volts), isdeveloped when the charges separate.

In a prior art, when energetic chemicals adsorbed on a thin conductorsurface, electrons with energies greater than a voltage barrier of about0.5 eV were detected in sensors similar to those represented by FIGS.1-A, 1-B and 2-A. However, the energy distribution decreasedexponentially beyond ˜0.1 eV, rendering the effect not useful for energyconversion and generation. Further, in those sensors the effectiveelectron mass of the metal conductor 10A, of order 1 m_e, is muchgreater than the effective electron mass in the semiconductor 11A,typically silicon, of order ⅓ m_e. This results in most of the generatedelectrons being reflected away from the semiconductor/metal interface15A, and therefore not collected. The relevance or utility of the roleof electron effective mass has not been disclosed or expanded. Thescheme also required the cryogenic cooling of the diode to reducethermal noise. The efficiency of this scheme is so low that current canonly be measured in the short circuit mode. The system can only be usedas a chemical sensor and is not a useful electric generator.

In a prior system, association reactions on or near a conductingcatalyst surface energized and initialized highly vibrational excitedmolecules. The energy of the vibrationally excited molecules wastransferred to the electrons in the conductor. The electron energy wasapparently in excess of a 1.2 volt barrier 11B. When a wide bandgapoxide semiconductor, TiO₂ was used, useful short circuit currents attemperatures well exceeding the boiling point of water, (up to 473Kelvin) are observed. Useful open circuit forward voltage was observedunder conditions of almost zero temperature gradient at roomtemperature. The forward voltage was similar to that observed in aphotovoltaicaly energized system using the same oxide semiconductor.

It would be highly advantageous to use a fabrication method resulting inpredictable high output voltages and currents, and to be able to choosematerials other than TiO2, to operate such a converter at an elevatedtemperature and to generate electricity in devices of this type usingthermal gradients.

The field of solid state thermionics uses thermal gradients to energizecharge carriers and uses semiconductor bandgap engineering to providevoltage barriers across semiconductor junctions. In such devices, chargecarriers must travel ballistically through the dielectric 11A. No chargecarrier ballistic travel is required in the material 10A. Moreover, itis acknowledged that charge carriers travel in all directions frommaterial 10A towards the dielectric 11A. The effects of a step increasein the carrier effective mass during ballistic transport has not beenused to enhance conversion efficiency and lower fabrication costs.

All known related converter concepts suffered an inefficiency directlyrelated to the unspecified and therefore uncontrolled relative chargecarrier effective masses of junction materials used. Nowhere does thefield claim nor profess to claim any method or knowledge of tailoring orcontrolling carrier effective masses to enhance energy conversionefficiency.

SUMMARY

A method and system for using pre-equilibrium ballistic charge carrierrefraction are disclosed. According to one embodiment, a devicecomprises one or more solid-state electric generators. The solid-stateelectric generators include one or more from the group including achemically energized solid-state electric generator and a thermionicsolid-state electric generator. A first material having a first chargecarrier effective mass is used in a solid-state junction of asolid-state electric generator. A second material having a second chargecarrier effective mass greater than the first charge carrier effectivemass forms the solid-state junction. A charge carrier effective massratio of the second effective mass divided by the first effective massis greater than or equal to two.

The above and other preferred features, including various novel detailsof implementation and combination of elements, will now be moreparticularly described with reference to the accompanying drawings andpointed out in the claims. It will be understood that the particularmethods and systems described herein are shown by way of illustrationonly and not as limitations. As will be understood by those skilled inthe art, the principles and features described herein may be employed invarious and numerous embodiments without departing from the scope of theteachings herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are included as part of the presentspecification, illustrate the presently preferred embodiment andtogether with the general description given above and the detaileddescription of the preferred embodiment given below serve to explain andteach the principles of the present teachings.

FIG. 1-A illustrates a prior art solid-state electric generator.

FIG. 1-B illustrates a prior art graph of potential versus distance andindicating the effect of a voltage barrier in a solid-state junction.

FIG. 1-C illustrates a graph of potential versus distance in anexemplary solid-state electric generator having a Schottky barrier.

FIG. 1-D illustrates a graph of potential versus distance in anexemplary solid-state electric generator having a p-n junction potentialbarrier.

FIG. 1-E illustrates a graph of potential versus distance in anexemplary solid-state electric generator having aconductor-dielectric-conductor nanocapacitor potential barrier.

FIG. 2A illustrates a prior art graph of potential versus distance,indicating the effect of heat in an energy conversion process.

FIG. 2-B illustrates a graph of potential versus distance in anexemplary solid-state electric generator where electrons experienceenergy loss to heat.

FIG. 2-C illustrates a graph of potential versus distance in asolid-state electric generator where heat re-energizes electrons to leakback across the junction.

FIG. 2-D illustrates a graph of potential versus distance in anexemplary solid-state electric generator with a heat sink.

FIG. 3-A illustrates an exemplary diagram of potential versus distancein a region where a pre-equilibrium ballistic charge carrier moves froma region of low charge carrier effective mass into a region of highcharge carrier effective mass.

FIG. 3-B illustrates an exemplary diagram of a single pre-equilibriumballistic charge carrier refracted into a concentrated angle of travelacross a junction

FIG. 3-C illustrates an exemplary diagram of multiple pre-equilibriumballistic charge carriers refracted into a concentrated angle of travel.

FIG. 3-D illustrates an exemplary diagram of multiple charge carriersreflected back towards the junction.

FIG. 4 illustrates an exemplary solid state electric generator usingdiode pre-equilibrium energy converter with pre-equilibrium ballisticrefraction and heat rejection.

FIG. 5 illustrates an exemplary solid-state, in-series, chemicallyenergized pre-equilibrium electric generator, according to oneembodiment of the present invention.

FIG. 6 illustrates exemplary electrically and thermally stacked thermalgradient converters using pre-equilibrium energy converters withballistic refraction.

FIG. 7 illustrates an exemplary cross section of a pillar structure onwhich pre-equilibrium ballistic refraction converters are attached.

FIG. 8 illustrates an exemplary cross section of a generalized pillarstructure that includes multiple forms such as corrugations, channels,pores and holes on which ballistic refraction converter assemblies areaffixed.

FIG. 9 illustrates an exemplary cross section showing reactant andcoolant flow from coldest (inside of structure) to hottest (outside ofstructure) on which pre-equilibrium ballistic refraction converterassemblies are affixed.

FIG. 10-A illustrates an exemplary cross section showing inert spacersformed along with ballistic refraction converter assemblies on asupporting substrate.

FIG. 10-B illustrates an exemplary cross section detail of a spacer andballistic refraction converter assemblies on a supporting substrate.

FIG. 11 illustrates an exemplary cross section showing stacking ofsubstrates containing ballistic refraction converter assemblies andshowing reactant, cooling and exhaust flows in the spaces betweenstacked elements.

FIG. 12 illustrates an exemplary cross section showing pre-equilibriumballistic refraction converter assemblies connected electrically inseries across the surface of a supporting structure.

FIG. 13 illustrates an exemplary cross section showing a substrate withreactant and coolants flowing through a supporting structure and aroundballistic refraction converter assemblies on the structure.

FIG. 14 illustrates an exemplary cross section of clusters electricallyconnected predominantly by tunneling and physically separated on anenergy converter.

FIG. 15 illustrates an exemplary addition of materials useful to managethermal conductivity issues into a low charge carrier effective massregion.

FIG. 16-A illustrates an exemplary device with minimal or no barrier inthe first material and an increasing charge carrier effective mass.

FIG. 16-B illustrates an exemplary device with minimal or no barrier inthe first material and the middle material having the lowest chargecarrier effective mass.

FIG. 16-C illustrates an exemplary device with a barrier in the firstmaterial and an increasing charge carrier effective mass.

FIG. 16-D illustrates an exemplary device with potential barriersagainst charge transport in both directions, and a minimum chargecarrier effective mass in the middle material.

FIG. 17 illustrates an exemplary cross section of catalytic acceleratorson pillars, thermally isolated nanoscopically and near active surface ofballistic refraction converter assemblies on a support structure.

FIG. 18 illustrates an exemplary surface containing ballistic refractionconverters and spacers being rolled, permitting reactant and coolantflow through the roll.

DETAILED DESCRIPTION

Methods, devices and systems for using pre-equilibrium ballistic chargecarrier refraction are disclosed. According to one embodiment, a methodcomprises fabricating one or more solid-state electric generators. Thesolid-state electric generators include one or more chosen from thegroup including a chemically energized solid-state electric generatorand a thermionic solid-state electric generator. A solid state electricgenerator energizes a pre-equilibrium energy distribution of chargecarriers in a first material having a first charge carrier effectivemass and forming a solid-state junction with a second material. Thesecond material has a second charge carrier effective mass greater thanthe first charge carrier effective mass. A charge carrier effective massratio of the second effective mass divided by the first effective massis greater than or equal to two.

In the following description, for purposes of explanation, specificnomenclature is set forth to provide a thorough understanding of thevarious inventive concepts disclosed herein. However, it will beapparent to one skilled in the art that these specific details are notrequired in order to practice the various inventive concepts disclosedherein. The present methods, devices and systems improve the energyconversion efficiency of junctions used in solid-state devices togenerate electricity. An energy source creates an unbalanced,pre-equilibrium energy distribution of charge carriers, e.g. electrons,on one side of a junction. When a net excess of charge carriers travelballistically and surmount an electrical potential barrier upon crossingfrom one side of a junction to the other, some of the charge carrierkinetic energy associated with motion is directly converted into anelectrical potential energy. Charge separation occurs and the regionsform a capacitor. In the absence of tunneling, only the velocitycomponent close to the normal to the potential barrier contributes tosurmounting the barrier.

The result is the conversion of some pre-equilibrium distribution ofenergy into the useful form of an electrically charged capacitor. A keyelement of the embodiments, the efficiency of this process is improvedwhen the directions of the charge carriers are refracted to travelsubstantially normal to the electrical potential by providing a materialwith an abrupt increase in the carrier effective mass across thejunction. Carriers ballistically traveling backwards, from high to lowcharge carrier effective mass regions may experience total internalreflection if they approach the junction from any angle greater than arelatively small critical angle. Backward flow tends to drain theseparated charges.

Energizing methods which cause a higher effective charge carriertemperature in a material with low charge carrier effective masscompared to the temperature of the high charge carrier effective massregion define a non-isothermal charge carrier distribution, and includetransient, pre-equilibrium distributions of charge carriers. Energizingmethods include using chemical reactions, using photovoltaic methods,using propagating and/or evanescent electromagnetic radiation, usingelectric coulomb coupling, using heat flow and associated thermalgradients, using solar energizers, using heat sources such asgeothermal, friction, and nuclear heat sources, using nuclearenergizing, using in-situ ionizing radiation, using radioactive wasteradiation, using flame heaters and catalytic heaters, usingpiezo-electric energizing and initializing highly vibrationally excitedreaction products using energetic chemical reactions.

According to one embodiment, the present system improves energyconversion efficiency by adding a charge carrier effective mass element.The element includes a nanoscopic ballistic carrier refraction effectinherent in ballistic charge transport from a region of lower chargecarrier effective mass into a region of higher charge carrier effectivemass.

The ratio of the charge carrier effective masses (m_e_high/m_e_low)determines the degree to which the ballistic charge carrier getsrefracted towards the potential barrier. This ballistic refractionmaximizes the charge carrier velocity component towards and directlyagainst the potential barrier and minimizes the other charge carriervelocity components transverse to the barrier. Minimizing the othercomponents minimizes energy losses. Ballistic transport is assured whenthe lower charge carrier effective mass region is thin enough to betransparent to charge carrier motion. The lower charge carrier effectivemass region forms a nano-layer electrode of the capacitor. The junctionof the low and high charge carrier effective mass regions forms acapacitor, which stores electrical potential energy as separatedcharges. The material with higher carrier effective mass is thedielectric of the capacitor.

According to another embodiment, heat transport across the junction isminimized. Ballistic refraction and a junction electrical potentialbarrier reflect heat-carrying charge carriers away from the junction. Inthe low charge carrier effective mass region, carriers with energy lessthan the barrier potential are reflected back into the hotter regionfrom whence they came. In the high charge carrier effective mass side,carriers approaching the junction with angles greater than therelatively small critical angle (relative to the surface normal) arereflected and can not travel backwards to the low charge carriereffective mass side.

Additional embodiments connect nanoscopic thermal gradient convertersthermally in parallel and/or in series and connect them electrically inparallel and/or in series. The connected converters are furtherconnected in parallel and/or in series. The thermal connections can bephysically distinct from the electrical connections. The energy and heatsources include those with unique, spatially non-uniform temperatureprofiles, temporally sporadic and non-constant energy bursts, andvarious regions may present non-uniform heat flow rates.

According to one embodiment, a secondary energy conversion process isused to extract electrical work by operating a solid statethermionic/thermoelectric heat engine between a higher temperature, suchas reject heat from a primary energy conversion process, and the coldertemperature heat sink of the ambient surroundings. Efficiency isenhanced by using pre-equilibrium ballistic charge carrier (e.g.electron) refraction (PEBCCR). Heat engine device components utilizingPEBCCR are nanoscopic thermal gradient converters (NTGC). Stackingnanoscopic thermal gradient converters in series thermally andelectrically provides an efficient way to implement a heat engine.

According to one embodiment, a system has successive converter units oneon top of the other, each converter unit having (a) conductor electrode,(b) low charge carrier effective mass region (also referred to as anano-layer electrode or nano-electrode), (c) high charge carriereffective mass region (also referred to as the dielectric) and (d)conductor electrode. One preferred embodiment of this nano-electrodecapacitor system forms element (b) from conductors such as metals thathave relatively long carrier mean free paths, such as Cu, Ag, Au, Al;forms material (c) using oxidized Ti metal to create n-type TiO₂; andforms material (a) and (d) from unoxidized Ti. Another embodimentincludes a heavily doped n-Si layer between the conductor electrode (a)and the nano-layer electrode (b). Another embodiment forms the element(b) using a heavily doped semiconductor such as n-Si or SiGe alloy. Theelectrical barrier of this junction is formed by the band offsets, whichare approximately 0.1 eV. This favors operation at the maximum powerdensity. Another embodiment includes a heavily doped n-Si layer betweenthe high charge carrier effective mass region (c) and the conductorelectrode (d).

According to one embodiment, the thickness of the region of lower chargecarrier effective mass is formed so thin that the carriers effectivelytravel predominantly ballistically. The lower charge carrier effectivemass region is formed with one or more materials with a lower thermalconductivity relative to electrical conductivity over nanoscopicdimensions. Materials with a favorable, enhanced, or high ZTthermoelectric figure of merit, values of ZT greater than approximately0.05, are generally considered to be at least favorable. The regionincluding the lowest charge carrier effective mass material with theother materials is referred to generally as low charge carrier effectivemass region.

The methods and systems may be used as a cooler or refrigerator uponapplication of a potential across the junction. The addition of PEBCCRincreases both the cooling efficiency and the cooling rate. The methodsand systems may be also be used to alter reaction rates.

One embodiment uses three-dimensional constructs and methods fortailoring heat transfer, cooling and power density and for increasingthe active area per volume (volumetric) to enhance the performance madepossible by ballistic carrier refraction.

According to one embodiment, using pre-equilibrium ballistic chargecarrier refraction enhances energy conversion efficiency in solid stateelectric generators. The embodiment includes a ballistic charge carriertransport from a region of lower charge carrier effective mass into aregion of higher charge carrier effective mass. A ratio of high to lowcharge carrier effective mass in excess of approximately 2 providesdesirable performance enhancement. An absolute high effective carriermass in excess of approximately 2 will generally provide acceptableperformance enhancement. The junction region materials are chosen suchthat a surmountable electrical potential is formed for charge carrierstraveling from the low charge carrier effective mass side to the highcharge carrier effective mass side. Any pre-equilibrium effectivetemperature gradient of charge carriers across the junction enables theenergy conversion.

Several configurations utilizing PEBCCR include devices energized by theproducts of chemical reactions, surface chemical reactions, interactionswith highly vibrationally excited molecules, thermal gradients, allforms of electromagnetic coupling such as propagating and/or evanescentradiation, in-situ energizing by nuclear radiation, or other methods.

Pre-Equilibrium Ballistic Charge Carrier Refraction Process (PEBCCRP)

One embodiment of the present teachings uses a combination of a stepincrease in the charge carrier (electron or hole) effective mass at amaterial junction and an electrical potential barrier at the junctionwhich tends to retard the charge carrier from traveling into thejunction, as shown generally in FIGS. 3-A thru 3-D. The step increase inthe charge carrier effective masses refracts the direction of ballistictravel towards the normal to the surface junction. Velocity componentstransverse to the normal are therefore diminished. In the solid state,these effects occur in the nanoscopic regime where transport isballistic and the dimensions are less than the charge carrier mean freepath, typically ˜1-50 nm and preferably >˜1 nm. Thickness dimensionsgreater than 1 nm can be acceptable. Thicknesses greater than 4 nm aredesirable. This is referred to as the pre-equilibrium ballistic chargecarrier refraction process (PEBCCRP). Devices or device components basedon PEBCCRP that convert thermal gradients to electrical potential arereferred to as nanoscopic thermal gradient converters (NTGC).

For example, as in FIG. 3-B, an electron crossing from a region of lowto a region of high electron effective mass changes direction towardsthe normal to the region of higher electron effective mass. This isequivalent to the Snell's law effect on light when traveling from aregion of low index of refraction (air) to a region of high index ofrefraction (water or glass), and the governing equations are the same.

One embodiment provides ballistic carrier refraction. Electronsgenerally move in all directions in a material. Electrons in the lowelectron effective mass material approaching the interface ballisticallyfrom any approaching direction all find themselves traveling nearlyentirely forward with a restricted range of angles into the region ofhigher electron effective mass, as shown in FIG. 3-C. Electrons in thehigh electron effective mass material ballistically moving backwardsinto the region of lower electron effective mass are reflected and cannot move back unless they approach with angles restricted inside thecritical angle, as shown in FIG. 3-D.

Recursive Pre-Equilibrium Ballistic Charge Carrier Refraction (R-PEBCCR)

One embodiment provides a method to recursively connect PEBCCRP and/ornanoscopic thermal gradient converter (NTGC) units where one end of therecursive system is the hottest and the other end of the recursivesystem is the coldest and attached to a heat sink. Connecting PEBCCRPand/or nanoscopic thermal gradient converter (NTGC) units allowsconversion of the heat flow at a higher temperature of a previous PECCRPunit in the recursive system to an electrical potential.

Charge Carrier Effective Mass Discontinuity for Chemically EnergizedPre-Equilibrium Electric Generators.

To enhance the energy conversion efficiency of chemically energizedpre-equilibrium electric generators, one embodiment of the teachingsuses the carrier effective mass discontinuity principle in choosing thematerial for the junction of lower charge carrier effective mass regionwith dielectric and electrical potential barrier higher charge carriereffective mass region. The conductor material is chosen such that itscharge carrier effective mass is as low as possible compared to thedielectric material whose charge carrier effective mass is as high asmaterial choices permit.

Thermal or Heat Rectifier

One embodiment provides a form of thermal isolation and the resemblanceto heat rectification. Almost all of the thermal conductivity in mostconductors is associated with (charge carrier) electron flow, not withphonon or lattice vibrations. The ballistic charge carrier refractionpermits charge carriers approaching from the low charge carriereffective mass side material to transport electrical energy, and henceheat, directly into the high charge carrier effective mass sidematerial. The total internal reflection in the high charge carriereffective mass side material greatly reduces electrical energy flowbackwards, and therefore also minimizes heat energy flow backwards.Consistent with the Second Law of Thermodynamics, this is analogous tothe total internal reflection of binocular prisms and certain reflectivecoatings used for thermal insulation.

Heat Sink and Energy Losses

One embodiment converts a fraction of the ballistic charge carriermotion into electrical potential energy. Energy conversion fromballistic charge carrier motion into electrical potential occurs whencharges are separated after surmounting an electrical potential barrier.The potential barrier can be formed in any one of many ways, forexample, a Schottky barrier, FIG. 1-C, a p-n junction FIG. 1-D and aconductor-dielectric-conductor nanocapacitor FIG. 1-E.

A forward biased diode provides one of the simplest methods to implementthis energy converting nano-layer electrode capacitor. FIG. 1-C depictsa forward biased Schottky diode whose positive terminal, a conductor, isthe nano-layer electrode and whose junction capacitance forms thecapacitor. FIG. 1-D depicts a forward biased p-n junction diode. Anano-layer electrode forms one side of the capacitor, the p-typesemiconductor forms the dielectric of the capacitor, and the n-typesemiconductor forms the other conductor of the capacitor. FIG. 1-Edepicts a conductor-dielectric-conductor capacitor, where the nano-layerelectrode forms one side of the capacitor and an insulator forms thedielectric of the capacitor. The devices can all be generally describedas energy converting nano-layer electrode capacitors.

In all these energy-converter nano-layer electrode capacitors,minimizing conduction across the capacitor in the forward bias directionincreases the efficiency of energy conversion. In contrast, a good diodemaximizes conduction in the forward bias direction.

One conduction property of a diode is characterized by the propertyreferred to as an “ideality factor”, “n”. The ideality factor of 1.0describes a theoretically optimized diode, and values greater than 1 areless ideal. The smallest n close to unity is best for a diode. Idealityfactors of 1.5 and greater generally reduce forward conduction and arenot generally regarded as “good” for a diode. A good capacitor requiresthe exact opposite of the diode and requires such minimizing ofconduction in the forward bias direction.

One way to minimize conduction of a forward biased diode used as anenergy-converter nano-layer electrode capacitor is to tailor the diodeideality property to be large to minimize the forward current.Minimizing forward current is achieved by favoring diodes with idealityfactors, n, greater than unity. Calculations show that diodes withideality as low as 1.2 can enable a 50 Celsius increase in reactiontemperature, which can result in an order of magnitude increase inreaction rates. Diodes with ideality >2 can enable more than 150 Celsiusincrease in reaction temperature.

Tailoring diodes to have relatively high generation-recombination (R-G)currents tends to result in ideality factors approaching n=2. Formingdiodes with a large state density due to metal interdiffusion anddangling bonds is a way to increase ideality. Forming diodes with highdefect density results in diodes with n>2. Diodes with significantPoole-Frenkel tunneling transport and trap-assisted tunneling transportboth increases n. Good diodes are not good capacitors, and vice versa.We emphasize the objective is to achieve the highest “fill factor” forthe energy conversion.

Thermionic models of Schottky diodes use “effective Richardson constant”as a multiplying factor for the diode forward current. Minimizing theeffective Richardson constant is also a way to minimize diode forwardconduction. The methods of our invention include the methods to maximizeideality and choosing semiconductors known to have relatively smalleffective Richardson constants, e.g. less than approximately 10amp/cm²-Kelvin². For example, TiO₂ has a Richardson constant less than0.05 amp/cm²-Kelvin²Kelvin². Using ballistic refraction in diodejunctions can be an effective method to reduce effective Richardsonconstants.

To tailor solid state junctions, bandgap engineering, degenerativedoping, doping gradients and composition gradients are effective inoptimizing the charge separation property of the junction. Potentialbarriers may be tailored to enhance tunneling and resonant tunnelingthrough the junction by narrowing and shaping the junction. Shapingincludes forming periodic or almost periodic electrical potentialbarriers using quantum well superlattice structures. Barriers may betailored to enhance carrier diffusion in the direction of chargeseparation by deliberately tailoring a sloping junction potential.

Embodiments remove reject heat in various ways, e.g. 3 D constructions.Embodiments stack and connect planar devices to maximize power density.

Pre-Equilibrium Ballistic Refraction Energy Converter

Referring to FIG. 4, one embodiment uses chemically energized,pre-equilibrium hot carriers as the first source of energy and convertsthe energy using pre-equilibrium ballistic charge carrier refractionprocess coupled with a heat sink. Another embodiment adds one or morestacked nanoscopic thermal gradient converters to convert reject heatfrom the chemically energized conversion step to electrical potential.

Referring to FIG. 4, chemical reactants in a region bounded in part by asurface 401 containing a catalyst may react in the vicinity of thesurface, may contact, adsorb, dissociate, recombine, or form reactionintermediates on, near or in the vicinity of the surface 401. Reactionstypically form highly vibrationally excited intermediates and products.Highly vibrationally excited products have been recently shown totransfer a major fraction of their vibrational energy directly to anelectron in the first conductor encountered.

One embodiment initializes highly vibrationally excited productsdirectly on or near a conductor to energize a pre-equilibrium ballisticrefraction energy converter conceptually shown in FIG. 4 and FIG. 5,505-508. In one embodiment, the catalyst conductor 505 is part of thedevice and promotes association reactions directly on or near thecatalyst conductor. As a result, highly vibrationally molecules areinitialized directly on or near the conductor 505. Approximately oneelectron per association reaction is energized with energy sufficient tosurmount 0.5-1.2 eV barriers in various conductor-dielectric junctions.The energy distribution of the ballistically transported electrons inthe conductor during the compressed phase of vibration is peaked aboutthe higher energies. Adsorbtion reactions are similar to molecularassociation reactions and result in similar energy transfer, but with anexponentially decreasing distribution. Charge transfer associated withprecursor mediated adsorbtions are associated with chargedintermediates, such as peroxo and superoxo adsorbates, which have shortresidence times on the surface and in some cases also energize and emitenergetic electrons. Highly vibrationally energized gas specie transfervibrational kinetic energy to energize electrons in the surfaceconductors 505.

The dielectric and electric potential barrier material 403 in thisdevice is chosen to have a large charge carrier effective mass, such assemiconductor TiO₂, compared to the conductor. TiO₂ is one of at leastseveral semiconductors known to have charge carrier effective massgreater than 2. The charge carrier effective mass of TiO₂ has beenmeasured under various conditions to be in the range 5-200 m_e, withprobable values ˜25 m_e. Therefore, nearly all the carriers energized inthe nano-electrode conductor 402 are refracted to have a directionnearly normal to the Schottky barrier formed by the conductor 402 andthe highest charge carrier effective mass material, e.g. TiO₂ dielectricsemiconductor 403. Electric potential is observed between negativeelectrode 406 and positive electrode 407. Both conductor and electrodematerials include materials chosen from the group including at least aconductor such as a metal, a conducting oxide, and degeneratively andheavily doped semiconductors such as heavily doped silicon, andsemiconductors, materials with a high ZT figure of merit. Heat generatedby the reactions and by the Schottky junction energy converter isrejected into a colder temperature heat sink 405.

The lower temperature heat sink may comprise the reactants 400themselves, because the reactants in this device are generally not hotwhen supplied to the system.

One embodiment includes using dielectric or semiconductor 403 other thanTiO₂ with higher than unity carrier effective mass, including but notlimited to, for example, rutile TiO2, anatase TiO2, porous anatase TiO2,SrTiO₃, BaTiO3, Sr_x-Ba_y-TiO_z, LiNiO, and LaSrVO₃, and certain organicsemiconductors, such as PTCDA, or3,4,9,10-perylenetetracarboxylicacid-dianhydride. The subscripts x, yand z denote concentrations, per usual conventions. One advantage ofSrTiO₃ is that Schottky barriers on it may be unpinned, providing arelatively larger barrier compared to that of TiO₂.

One embodiment includes providing a direct heat sink 405 to thedielectric 403. Such heat sinks can include but are not limited to heatpipes, capillary systems with fluid flow, evaporative cooling includingbut not limited to using reactants themselves, heat conductive materialsand convective flow methods, and a nanoscopic thermal gradientconverter.

Nanoscopic Thermal Gradient Converter (NTGC)

One embodiment is a device based on the pre-equilibrium ballistic chargecarrier refraction process: a nanoscopic thermal gradient converter. Inone embodiment, shown in FIG. 5, elements 501-503 are a SurfaceNanoscopic Thermal Gradient Converter (SNTGC), while element 703 of FIG.7 is a Volumetric Nanoscopic Thermal Gradient Converter (VNTGC). Thejunction providing an electrical retarding potential between thematerials may include at least a conductor-dielectric,dielectric-dielectric, or a dielectric-conductor-dielectric junction.Insulators and semimetals are considered subsets of dielectrics andmetals here. Elements 501-503 of FIG. 5 show an example schematic layoutof conductor-semiconductor junction in a nanoscopic thermal gradientconverter.

The term “semiconductor junction” includes semiconductor junctions,junctions including quantum wells formed of metal and/or semiconductor,insulator materials with a large bandgap and low doped and amorphousmaterials, semimetal, insulator, amorphous material, polycrystallinematerial. The term “metal” includes heavily doped semiconductors, metal,semimetal, heavily doped semiconductor, electrical conductor. In all thecases related to pre-equilibrium charge carrier ballistic refractionenergy conversion processes, the guiding principal is that the junctionpresents both a retarding and surmountable and/or tunneling potential tothe approaching ballistic charge carrier, and an increase in carriereffective mass.

Referring to FIG. 5, one embodiment adds a nanoscopic thermal gradientconverter 501-503 to the chemically energized pre-equilibrium electricgenerator 505-508. Heat 500 rejected by the hotter, chemically energizedpre-equilibrium electric generator 505-508 (the primary energyconversion system), energizes electrons at the input side 501 of thenanoscopic thermal gradient converter 501-503 (the secondary energyconversion system). In a configuration including other primary energyconversion systems in general, nanoscopic thermal gradient convertersare connected in series thermally and electrically. This interconnectionreferred to as “series-parallel” does not preclude series parallelconfigurations used to assure reliability. For example, the negativeelectrode 508 of the chemically energized generator is electrically andthermally coupled to the positive electrode of low charge carriereffective mass region 501 of the nanoscopic thermal gradient converter.The negative electrode 503 and the high carrier effective mass material502 of the thermal gradient converter are coupled thermally to thecolder, heat sink 510. Electricity is taken from the positive electrodeof 506 and the negative electrode 503, and because the devices are inseries for this example, also from positive electrode of 501 andnegative electrode 503. Note the output voltage may be tapped from anyof the positive and negative electrode pairs. Note that such multipleoutputs are highly advantageous.

This configuration permits the chemically energized generator to operateat a higher catalyst temperature than without the nanoscopic thermalgradient converter, permitting an increase in reaction rates andtherefore higher power density. The increased temperature also permitsuse of a wider range of reactants and operation at the ignitiontemperature of some reactants.

Recursive Nanoscopic Thermal Gradient Converters

Referring to FIG. 6, one embodiment recursively repeats nanoscopicthermal gradient converters, each connected in series to the next bothelectrically and thermally. The first stage 601 can be an electricgenerator energized by any of the many known methods

The recursively repeated nanoscopic thermal gradient converters 602 thengenerate electricity from the higher temperature reject heat of thefirst stage 601 and the lower temperature ambient heat sink. Estimatessuggest that a recursively repeated nanoscopic thermal gradientconverter can achieve ˜80% of the Carnot limit efficiency between itsheat source and heat sink temperatures.

Note again, an output voltage may be tapped from any of the positive andnegative electrode pairs.

Ballistic Refraction Energy Converters

One generalized embodiment is the surface ballistic refraction energyconverter. Another is the volumetric ballistic refraction energyconverter. Other forms and combinations may also be used.

The term “volumetric” refers to configuration where the active surfacesand reactant and coolant flow channels are formed on or using threedimensional structures.

Surface Ballistic Refraction Energy Converter (SBREC)

One embodiment uses a primary energy converter attached to a series ofsecondary nanoscopic thermal gradient converters attached to a heatsink. FIG. 6 shows such a typical surface ballistic refraction energyconverter. A number of secondary nanoscopic thermal gradient converters602 are connected in series. One end of the series 602 is attached to aheat sink 603. The other end of the series 602 is connected to a primaryenergy converter 601 based on the pre-equilibrium ballistic chargecarrier refraction process. The primary energy converter may beenergized by chemical reactions, thermal gradients, photo-voltaic orother means. The number of components 602 may be from 0 to a desirednumber, both inclusive. The main function of the components of 602 is toconvert a fraction of the reject heat energy from the previouslyconnected energy conversion component to an electrical potential.

One embodiment includes a primary converter 601, with a step increase incharge carrier mass between the junction materials, where the electronsare energized by chemical reactions on or near the conducting surface,with 0 to desired number of nanoscopic thermal gradient converters 602connected in series electrically and thermally and attached to a heatsink.

One embodiment includes a primary converter 601, without a step increasein charge carrier mass between the junction materials, where theelectrons are energized by chemical reactions on or near the conductingsurface, with one to a desired number of nanoscopic thermal gradientconverters 602 connected in series electrically and thermally andattached to a heat sink.

One embodiment includes a primary converter 601, using a photo-voltaicenergy source with or without the step increase in charge carrier massbetween the junction materials, and with one to a desired number ofnanoscopic thermal gradient converters 602 connected in serieselectrically and thermally and attached to a heat sink.

One embodiment includes a primary converter 601, a thermionic energyconverter where charge carrier ballistic transport occurs in the firstmaterial instead of the second material, with zero to a desired numberof nanoscopic thermal gradient converters 602 connected in serieselectrically and thermally and attached to a heat sink.

One embodiment includes a primary converter 601, a thermionic energyconverter with a second material effective charge carrier mass greaterthan the first material charge carrier mass, with 0 to desired number ofnanoscopic thermal gradient converters 602 connected in serieselectrically and thermally and attached to a heat sink.

One embodiment includes a primary converter 601, a thermionic energyconverter with a second material effective charge carrier mass greaterthan the first material charge carrier mass and where charge carrierballistic transport occurs in the first material instead of the secondmaterial, with 0 to desired number of nanoscopic thermal gradientconverters 602 connected in series electrically and thermally andattached to a heat sink.

One embodiment includes a primary converter 601, attached to a series ofnanoscopic thermal gradient converters 602, one or more of which mayinclude a dielecrtic-conductor-dielecrtic junction for the regiongenerally referred to as the low carrier effective mass region, andconnected in series electrically and thermally and attached to a heatsink. The number of nanoscopic thermal gradient converters may be from 0to the number desired, both inclusive.

Volumetric Ballistic Refraction Energy Converter (VBREC)

One embodiment includes volumetric ballistic refraction energyconverters on a pillar-like form. A desirable feature of the pillar is ahigh area per length, which results in a high volume power densityresulting from the pillar's relatively large area per volume. The crosssection of such a high area pillar may include deep corrugations, holesand pits, all of which may be irregular. The cross section of a pillaris limited mainly by the constraints imposed by the converters formed onit and has no general constraints. For example, the cross section may beany combination from the group including at least: wire-like, circular,bar-like, square, rectangular, irregular, wrinkled, sponge-like, atruncated cone, a tapered cone, and a cross section like that of wingsor other aerodynamic forms.

Referring to FIG. 7, the pillar itself 701 can be can be any material,such as strands, fibers, strips formed with one or more materials eachchosen for their strength, thermal conductivity, electricalconductivity, or any other desirable property.

A pillar would first be at least partly coated with a conductor 702 toform the back electrode of the device. Then as many as requiredsecondary nanoscopic thermal gradient converters 703 are formed over thepillar and under a final primary energy converter 704, with or without astep increase in charge carrier mass between the junction materials. Theprimary energy converter 704 may be energized either chemically,photo-voltaically, by thermal gradients or other means. The outer region705 is the source energizing region. The number of units 703 range fromzero to the required number, both inclusive. The positive electrodeconnection 706 is in electrical contact with the final converter 704. Aninsulator 707 separates the positive electrode connection 706 from thenegative electrode connection 708, which is in electrical contact withthe conductor 702. Heat sink can be provided by the reactants and gassessurrounding the pillar region 705 and or by the substrate 709 which canbe physically connected to a heat sink.

One embodiment includes a primary converter 704 where the electrons areenergized by chemical reactions on or near the conducting surface, with0 to a desired number of nanoscopic thermal gradient convertersconnected in series electrically and thermally and attached to a heatsink.

One embodiment includes a primary converter 704, a photo-voltaic energyconverter with 0 to a desired number of nanoscopic thermal gradientconverters connected in series electrically and thermally and attachedto a heat sink.

One embodiment includes a primary converter 704, a thermionic energyconverter with 0 to a desired number of nanoscopic thermal gradientconverters connected in series electrically and thermally and attachedto a heat sink.

One embodiment includes long mean free path semiconductors as well aslong mean free path metals as the materials forming the minimum chargecarrier effective mass region. Band gap alignments may be used to formpotential barriers.

One embodiment includes a primary converter 704, a solid state thermalgradient energy converter using a dilectric-conductor-dilectric junctionattached to a series of similar nanoscopic thermal gradient convertersconnected in series electrically and thermally and attached to a heatsink. The number of nanoscopic thermal gradient converters may be from 0to the number desired, both inclusive.

In general, ballistic refraction energy converters can be attached tovarious kinds of objects, including to devices used to cause reactantflow, air flow, and cooling, such as such fan blades. It can take theform of a sheet following the contour of the objects. For example, theconverters can be “coated” on to the air flow system. Alternatively, theconverters can be separately made and “pasted” on to the system. Or,they can be integral to the system.

Placing ballistic refraction energy converters directly on the fan blademaximizes the efficiency with which the fan provides cooling, heattransfer and heat removal.

As suggested by FIG. 8, ballistic refraction energy converters 801affixed to the pillar with cross section profile 802 may be any shapeconsistent with the requirements for making the ballistic refractionenergy converters. A large energy collection area is desirable and maybe achieved in many ways, including forming the profile to include long,thin forms 802, wedges 803, channels 804, irregular polygonal sides 805,deep narrow channels or pores 806, pores that completely go through thepillar 807, symmetric forms 808 and 803, almost symmetric forms 809, andsmoothly symmetric forms 810.

Pores can take the form of deep holes into the stack 804, or as holesthat go entirely through the stack 807.

Wire Geometry

One embodiment forms a converter geometry resembling a long thin devicesuch as a wire 802. The converter wire can be preformed and poked intothe surface or otherwise attached to the surface in regular or irregularpatterns.

Flow Geometry

One embodiment provides a heat sink for ballistic refraction energyconverters. A heat sink for cooling can be achieved in many ways,including by convective flow, phase change or evaporative cooling, andheat pipes. Reactants or reactant components may be used. For example,FIG. 9 illustrates an embodiment using channels, ducts or pipesassociated with the structure supporting the converters and with theinterior of the converter assembly, through which coolant may flow,reactants may flow, additives may flow, or any combination of thesematerials may flow. Each case has its advantages. Materials 901 flowfrom the colder side 902, through pores or holes 903 to the hot region904. Both the cold side 902 and the hot side 904 may include reactantsor additives, and the hot side is associated with both exhausts and airflow.

Evaporation of reactants 901 on the cold side 902 as well as the flow ofcolder materials 901 causes cooling. Reactants 901 can be concentratedand fuel rich near the stack hot surface 905.

Using liquid reactants or evaporative coolant 901 that becomes gas uponcontact with warmer, reaction surface 905 provides a desirable gasspecie for chemically energized hot electron processes.

One embodiment forms converters directly on aerodynamic surfaces. Thispermits both direct generation of electricity as well as using the gasgenerated by the liquid-gas transformation as mass flow to push aturbine or other mechanical extraction of useful work and generation ofshaft energy.

One embodiment uses liquid air and other liquid gasses 901 for their lowtemperature heat sink in an electric generator. Liquid air and similarinert liquid gasses may provide a heat sink to the region 902, theambient air in the exhaust region 904 may provide the heat source, andthe device may thereby generate electricity directly using thetemperature difference. The liquid/gas phase transition may also operatea mechanical energy converter such as a turbine, at the same time.

One embodiment uses natural convection to provide air flow. It is notedthat the cooling air volume can typically be orders of magnitude greaterthan the reaction air volume.

One embodiment based on FIG. 9 may also represent the cross section ofgeneralized tube geometry, such as flattened tubes. A generalized tubeis coated on one or more faces with ballistic refraction energyconverters. “Tube” here refers to something with any partly hollowgeometry, with any relative wall thickness, including non-uniform walls.For example, a tube can be flattened so that it looks like two sheetswith an enclosed space between them to allow gas or fluid flow and withthe volume enclosed at the edges. Note that the concepts of FIG. 9 couldbe used in surface as well as volumetric devices (SBREC and VBREC).

Stacking Geometry

Referring to FIG. 10, an elementary stackable unit is placed on astructure that includes one or more of the electrically conductinglayer, thermally conducting layer, and the structural support layer.

Embodiments connect and stack together more than one ballisticrefraction energy converter (surface (SBREC), or volumetric (VBREC))assembly to create a volume of electric generators instead of just anarea provided by the surface of a single converter assembly. The stackscan be connected electrically in series or parallel.

One embodiment of an elementary stackable unit, shown in cross sectionin FIG. 10, includes the key element: ballistic refraction energyconverter assembly 1001 (which may comprise of primary only or primaryand secondary energy converters) to be connected electrically withpositive and energized side 1004 up and negative side down. Theballistic refraction energy converters are supported and connected withpositive electrode connection 1002, negative electrode connection 1003.Structure 1003, which may include one or more of an electricallyconducting element, a thermally conducting element and a strengthstructure element. Stacking involves placing the elementary stackableunit on top of other elementary stackable units, leaving a space abovethe active surface of the converter 1001 for energizing and heatsources. The same may be accomplished in any workable configuration orarrangement.

The embodiment shown in FIG. 10 connects the positive electrode 1002 tothe negative electrode 1003 of the converter above it. A cross sectionof this is shown in FIG. 11. Note that each elemental structure of FIG.11 may be recursively stacked in the vertical and/or in the horizontaldirection to form a matrix of the three-dimensional elemental stackedstructures.

FIG. 10-b provides detail related to electrical and thermal connectionsand interfaces that have been deliberately left out for clarity in theembodiments.

Referring to FIG. 10-b, for example, the positive electrode-1002 wouldnot be directly placed on the active surface of the converter 1001 asshown because the active surface is typically a nanometers-thickstructure that is easily damaged. In practice, those generally skilledin the art would use one of many known methods to connect the electrodeto the converter. One embodiment places the positive electrode 1002 onan insulator 1005 formed directly on the structure 1003 and then anelectrical bridge 1006 is formed to electrically connect the positiveelectrode 1002 to the positive end and active surface 1004 of theballistic refraction converter assembly. The structure element 1003would in practice include an electrical conductor connected to thenegative side of the converter and would also include a thermalconnection to the converter. A simple embodiment forms the structure1003 to be both electrically and thermally conducting, for example a 5micron thick aluminum or copper foil.

One embodiment stacks the elementary stackable units shown in FIG. 10 ontop of each other, forming a volume of electric generator energyconverters. Reactants and coolants 1100 flow into the spaces 1101between the stacks and exhausts flow out through the spaces.

One embodiment connects the converters in series along the plane of thestack by connecting the positive electrode to the negative electrode ofadjacent converters in the same plane. This can be accomplished severalways, one of which is shown in FIG. 12. An electrical connection 1202 ismade to the positive side and active surface of a first converter 1201and is connected to an interconnecting conductor 1203 isolated byinsulators 1204. The interconnect 1203 electrically contacts thenegative side 1205 of a second converter. The insulating spacer 1200 isshown conceptually behind a converter in the figure.

One embodiment provides coolants and/or reactants 1300 through the bodyof an elementary stackable unit, as sketched in FIG. 13. For example,ballistic refraction energy converters 1301 and spacers 1302 are formedon a structure and substrate 1303 inside of which 1304 flow reactantsand/or coolants 1300. Referring to FIG. 18, the device of thisembodiment can be rolled up and the spaces 1305 between the roll formedby spacers 1302 permit reactants to flow into and exhausts can flow outof the spaces 1305. The spacers and electrical interconnects are shownin FIG. 13 for clarity. Detailed connections could also be like thoseexplained in FIG. 12 and FIG. 10-b.

In each of these embodiments, the converters can take on many forms,including the pillar forms described above, and can be attached on manysurfaces of nearly arbitrary shapes.

Tunneling Cluster Catalysts

One embodiment uses physically disconnected, electrically tunnelingconnected nanoscopic catalyst clusters to enhance the effectivetemperature gradient of excitations on the active surface of a ballisticrefraction energy converter. FIG. 14 schematically shows conductorcatalyst structures 1400 with typical dimension D and typical separationS on the converter 1401 with active surface 1402. The dimension D isformed to be less than the mean free path for hot carriers in thecluster 1400, chosen to allow the carrier transit time to be shorterthan the period of the highest lattice vibration of the cluster 1400 andhence decouples carrier temperature from lattice temperature. Thisdimension is typically in the range of order 4 to 50 nm in materialssuch as Cu, Ag, Au, Pd, and Pd. The cluster separation D is chosen to besmall enough to permit charge carrier electron tunneling betweenclusters 1400. This dimension is typically in the range 1-20 nm.Electrical connections to the cluster are formed by electrical conductorcontacts 1403 and 1404. In an ideal case, the disconnected clusters areformed on a low electrical conductivity and low thermal conductivitymaterial. This cluster arrangement can then form a Schottky barrier withthe converter 1401, permitting the clusters to be an integral part of aballistic refraction energy converter.

One embodiment uses the enhanced catalyst activity of catalyst clustersin contact with ceramic substrates such as converter material. Oneembodiment uses the enhanced cluster electron temperature to increasereaction rates and therefore increased power output. One embodimentapplies an electrical potential across electrodes 1403-1404, which hasbeen shown to heat the clusters to temperatures (˜2000 K-5000 K) far inexcess the substrate temperature (˜300 K) and hence can greatly increasereaction power without increasing converter diode temperature.

Coupling and Conversion Layers

One embodiment uses a quantum well superlattice for the lowest chargecarrier effective mass material. To maximize conversion efficiency, thesuperlattice is tailored such that it filters carriers with energiesslightly greater than the barrier height from the low carrier effectivemass region to the high carrier effective mass region.

One embodiment forms closely spaced buss bars on the active surface tominimize ohmic losses across the surface. Chemically inactive buss barsare formed as close as 100 nm apart, with active material such astunneling cluster catalysts between the buss bars.

One embodiment uses very thin semiconductor for the barrier-presentingmaterial. The minimum thickness is typically of order 5 nm. A preferablesemiconductor thickness is in the range between 20 and 100 nm althoughother thicknesses are contemplated.

Thermal Conductivity Management

Referring to FIG. 15, one embodiment tailors the lower charge carriereffective mass region 1500-1501 to include elements for controlling andlimiting the transfer of heat, and enhancing the transfer of chargecarrier kinetic energy. These elements include one or more of lowthermal conductivity materials, long carrier mean free path materials,thermal diode elements, quantum confinement elements and graded carriereffective mass elements. The principle is to present multiple regions ofincreasing carrier effective mass to the charge carrier as it travelsballistically towards the barrier region. FIG. 15 show two such regions1500, 1501.

Referring to FIG. 15, one embodiment uses a semiconductor (S) 1500 witha charge carrier effective mass as low as practical, such as siliconwith a charge carrier effective mass ˜0.3 m_e in contact with aconductor (C) 1501 with a higher charge carrier effective mass and knownto have unusually long electron mean free paths at ˜1 eV. Suchconductors 1501 include, for example, Au (˜20-100 nm), Ag (˜20 nm) andCu (reported as high as 60 nm) and Al (˜20 nm). A ballistic chargecarrier refraction effect then exists between the semiconductor 1500 andthe conductor 1501. The semiconductor 1500 may then inject its hottercharge carriers via a narrow range of directions into the conductor C1501. The conductor C 1501 is chosen to have a thickness less thanapproximately 2 times a charge carrier mean free path. Nearly all chargecarriers traveling through the conductor C 1501 are already directedtowards the semiconductor S_barrier 1502, for example TiO₂ with chargecarrier effective mass ˜25 m_e, higher than 1501 charge carriereffective mass.

Materials with electron effective mass less than 1.1 and materials withrelatively long electron mean free paths can be used for eithersemiconductor 1500 or lowest charge carrier effective mass material1500, including, but not limited to: air, aluminum, conducting carbonnanotubes, conductors, copper, degeneratively doped materials, gasseousmaterial, gold, metals, metals, molybdenum, nickel, palladium, platinum,rhodium, ruthenium, silver, tantalum, vacuum. The materials with a ZTfigure of merit greater than approximately 0.05 and generally preferredfor thermoelectric applications may also be used for lowest chargecarrier effective mass material 1500, including but not limited to:aluminum antimonide (AlSb), aluminum arsenide (AlAs), aluminum galliumnitride (AlxGa1-xN), bismuth selenide (Bi2Se3), bismuth telluride(Bi2Te3), and boron nitride (BN), gallium aluminum arsenide (GaxAl1xAs), gallium aluminum arsenide antimonide (GaxAl1 xAs1 y), galliumantimonide (GaSb), gallium arsenide phosphide (GaAsyP1 y), galliumarsenide, gallium indium antimonide (GaxIn1-xSb), gallium indiumphosphide (GaxIn1 xP), gallium nitride (GaN), gallium phosphide (GaP),germanium (Ge), indium aluminum arsenide (InxAl1 xAs), indium antimonide(InSb), indium arsenide (InAs), indium arsenide phosphide (InAsyP1-y),indium gallium aluminum arsenide (InxGyAl1 x yAs), indium galliumarsenide (InxGa1-xAs), indium gallium arsenide antimonide (InxGa1xAsySB1 y) indium gallium arsenide phosphide (InxGa1 xAsyP1 y), indiumgallium nitride (InxGa1-xN), indium phosphide, lead telluride, lead tintelluride (Pbx Sn1 xTe), mercury cadmium selenide (HgxCd.1 xSe), mercurycadmium telluride (HgxCd1-xTe), silicon germanium, silicon, zincselenide (ZnSe), zinc telluride (ZnTe), where the subscripts x, y, z,1-x, and 1-y denote the relative amounts of the atomic species in eachternary or quartenary materials and range from zero to one, inclusive.

The barrier-presenting layer 1502 may be made from materials includingbut not limited to semiconductors known to have carrier effective massesgreater than 2, including but not limited to: rutile TiO2, anatase TiO2,porous anatase TiO2, SrTiO3, BaTiO3, Sr_x-Ba_y-TiO_z, LiNiO, LaSrVO3,organic semiconductors PTCDA,(3,4,9,10-perylenetetracarboxylicacid-dianhydride). The followingmaterials and semiconductors with at least favorable ZT figure of meritsand generally preferred for thermoelectric applications may also be usedwhen their charge carrier effective masses are greater than two timesthat of the material chosen for their junction, including but notlimited to: aluminum antimonide, aluminum gallium arsenide, aluminumoxide, bismuth selenide, bismuth telluride, boron nitride, galliumaluminum arsenide antimonide, indium aluminum arsenide phosphide, indiumgallium alluminum nitride, indium gallium arsenide antimonide, indiumgallium arsenide phosphide, lead europium telluride, lead telluride, andair. lead tin telluride, mercury cadmium selenide, mercury cadmiumtelluride, silicon germanium, silicon oxide, zinc selenide, zinctelluride.

The conductor becomes more like an insulator against heat energytransport, on the timescale of ballistic transport, and a very good, onedirectional conductor for charge carrier energy transport in the presentthermoelectric and thermionic energy converters. Within this nanoscopicdimension the conductor can sustain a useful temperature gradient acrossit. The thermal isolation of the nanoscopic sandwich 1500-1501-1502increases the efficiency of the electric generator process.

The addition of a low charge carrier effective mass material, aconductor 1501, between a lower charge carrier effective mass material1500 (with values as low as 0.02 m_e), and a highest charge carriereffective mass material 1502 (with values as high as 200, m_e, such asTiO₂), expands the range of materials that may be used in a solid stateenergy converter.

One embodiment includes catalyst clumps 505 physically isolated andelectrically connected through electron tunneling. The clumps 505replace at least some and in some configurations the entire conductor506 on the surface of an electric potential barrier (dielectric)material 507.

Another embodiment uses such nanoscopic constraints on the dimension ofconducting catalyst clusters, sheets, nano-wires, nano-dots, nano-tubes,quantum dots, layers and constructs 505 to enhance reaction rates inchemically energized pre-equilibrium energy converters.

Tailoring Charge Carrier Thermal Coupling

According to one embodiment the energy transfer between materials incontact with the heat or hotter electron source and the colder regionare controlled to be predominantly by ballistic charge carriertransport. Referring to FIGS. 16-A through 16-D, we show a cross sectionof a device using three materials or regions. As a general governingprinciple, the first and second regions, 1601 and 1602, are designed toblock heat and transmit energized, ballistic carriers with minimalenergy loss. The ideal condition is the transport of energy only byballistic electrons (charge carriers) and not by heat, from region 1601,1602 to region 1603. As a general governing principle, third region 1603is designed to pass only the more energetic ballistic charge carriersagainst and over an electrical potential barrier, and to refract thedirection of the ballistic carriers so they transport directly into thepotential. The refraction is enhanced when the third region 1603 has acarrier effective mass at least two times higher that of the conductorregion 1602, and is overwhelmingly so when it is higher by at least afactor of 2. The first and second regions 1601, 1602 are generallycharacterized by a favorable ZT thermoelectric figure of merit. Thesecond region 1602 is generally characterized by an enhanced tendency totransmit a large number of ballistic electrons, and this is generallyreferred to as having a relatively long mean free path.

The first material 1601 may have a higher, equal or lower charge carriereffective mass than the second material 1602. In addition, the firstmaterial 1601 may or may not present an electrical potential barrier tocarriers traveling, backwards from the second material 1602 back intothe first material 1601. These two options result in four cases, eachcase having relative advantages. The choice depends on materialavailability, manufacturability, cost, stability and other factors.

One embodiment including the first case FIG. 16-A, with minimal or nobarrier in the first material and an increasing charge carrier effectivemass from left to right 1601, 1602, 1603, offers the fastest andshortest path transfer of energetic electron energy into the barriermaterial with highest charge carrier effective mass 1603. Nearly any ofthe common semiconductors may be used as the first material becausevirtually all of them are commercially valuable precisely in partbecause their charge carrier effective masses are all low, less than 1m_e. This means that all the known favorable ZT materials can be usedvery effectively. A minimal barrier can be achieved by band gapengineering or degenerative doping.

One embodiment including the second case FIG. 16-B, with minimal or nobarrier in the first material 1601 and since the middle material 1602has the lowest charge carrier effective mass, it allows charge carriersin the middle material to exit the material more easily than allowingentry of charge carriers from materials 1601 and 1603. For example,electrons that have energies too low to surmount the barrier in material1603 are not only reflected back into middle material 1602 but also arequickly transported to the warmer material 1601 for reheating andreprocessing. The middle, inner region 1602 is electronically, andtherefore in the case of ballistic transport, thermally isolated to theouter regions 1601, 1603. This tends to minimize energy transfer fromelectrons to lattice, which in turn minimizes heat conductivity losses.The back-to-back ballistic refraction tends to isolate the two heat bathregions 1601 and 1603.

One embodiment including the third case FIG. 16-C, with a barrier in thefirst material 1601 and an increasing charge carrier effective mass,provides fastest transport of only the hottest charge carrier of thefirst material 1601.

One embodiment including the fourth case FIG. 16-D, presents electricalbarriers against charge carrier transport back into the hotter material1601 and into the colder material 1603, and has the minimum chargecarrier effective mass in the middle material 1602. This configurationalmost reversibly communicates carrier energy between two heat baths,which is a key property, and because of the ballistic transport, andpreferentially transports charge carrier energy faster than by latticephonon or other energy transfer. Note that ballistic transport is onlynecessary in the middle region 1602 and not in the surrounding regions1601, 1603. The charge carrier may be negative or positive, and thebarriers are designed to retard transport. Example materials for theregions can be, for example, TiO2 for the outer regions and Silicon forthe middle region, where band gap alignments provide the barrier. Themiddle region 1602 materials can be chosen from the group including atleast metals with long mean free paths, such as Cu, Au, Ag, Al, andmaterials with high ZT.

One embodiment uses the same barrier region material on both sides ofthe conductor.

One embodiment to use thermally energized ballistic refraction energyconverters as refrigerators utilizes one or more stacked converters andapplies a positive potential across the terminals instead of thenegative potential obtained from the same device used as a generator.The heat sink may then be hotter than the heat source, and coolingoccurs because the hot electrons are efficiently removed from the cooledregions. The use of ballistic refraction enhances the efficiency of sucha cooling method and device over devices where carriers are not directedpredominantly into the potentials at the interfaces of low and highcharge carrier effective mass materials.

Embodiments form one or more refrigerating ballistic refraction energyconverters directly on integrated circuits to cool them. A similarembodiment forms a refrigerating ballistic refraction energy converterdirectly on chemical reaction surfaces, for example, to control reactionpathways and control reactions.

Fuels, Oxidizers, Autocatalysts, Stimulators

Embodiments use storable reactants including oxidizers, autocatalyticreaction accelerators, decelerators, and monopropellants. The liquidphase, such as liquid hydrogen peroxide H₂O₂ at standard pressure andtemperature, are convenient because their heat of vaporization is usedas coolant and the liquid is conveniently storable. Monopropellants suchas H₂O₂ and monomethylhydrazine (MMH) are similarly convenient andenergize the active surface of converters. Autocatalytic acceleratorsinclude monopropellants such as H₂O₂.

One embodiment uses thermally isolated catalysts in close proximity tothe active surface of ballistic refraction converter assemblies toenhance reaction rates and concentrate thermally hot entities to thethermally hot region of the converter.

FIG. 17 shows an embodiment where a highly reactive catalyst 1701 isplaced on a thermally isolated pillar structure 1702 in close proximityto the active surface 1703 of a converter. Gas phase reaction productscreated in the vicinity of the catalyst energize the converter. Theproducts may include one or more of at least highly vibrationallyexcited molecules, reactive molecules, and hot gases.

Embodiments use energetic reactants chosen to maximize the energizing ofhighly energetic specie, which include one or more of highlyvibrationally excited molecules (HVEM), hot atoms, charged adsorbateintermediates such as peroxo and superoxo specie formed during precursormediated dissociative adsorbsion, adsorbates participating inassociation reactions both of the Langmuir-Hinshelwood and of theEley-Rideal type, and reaction intermediates such as radicals, freeradicals and specie considered to be catalytic or autocatalytic.

Embodiments provide means for the energizing to occur directly on or inthe vicinity of a conductor. The term “vicinity” refers here to adistance less than a few mean free paths of the particular energeticexcitation. Embodiments use these excitations to energize a low chargecarrier effective mass material of the ballistic refraction energyconverter.

Chemical reactions using reactants of this kind result inpre-equilibrium excitation including reaction effective temperatures andeffective carrier temperatures in excess of 10,000 Kelvin on and inmetals, conductors, catalysts, semiconductors and ceramics, and wherethe carriers include excitons, carriers in the conduction and/or valenceband of semiconductors and insulators.

One embodiment uses reactions and reactants to energize theseexcitations. The reactions, reactants and additives include at leastmonopropellants, high energy fuels with oxidizers, hypergolic mixtures,and additives and combinations of reactants known to produceautocatalytic specie, reactants chosen to accelerate reactions or tocontrol reactions, and combinations thereof. The reactants and/oradditives include but are not limited to the following reactants:

TABLE I energetic fuels more storable than ammonia amine substitutedammonias Di-Methyl-Amine (CH₃)₂NH Tri-Methyl-Amine (CH₃)₃NMono-Ethyl-Amine (C2H5)NH2 Di-Ethyl-Amine (C₂H₅)₂NH) other classes moreeasily storable Methanol, CH₃OH Ethanol, EtOH CH3CH2OH Formic Acid,HCOOH diesel fuels gasoline alchohols slurries including solid fuelsCarbon Suboxide, C₃O₂, CO═C═CO, Formaldehyde HCHO, Paraformaldehyde, =better HCHO)_(n), sublimeable to Formaldehyde gas. (Potentially a cellcoolant at the same time). less storable fuels Carbon Monoxide HydrogenAmmonia NH3 energetic fuels containing Nitrogen Nitromethane, CH₃NO₂Nitromethane “cut” with Methanol = model airplane “glow plug” enginefuel High energy fuels with wide fuel/air ratio Epoxy-Ethane, = Oxiraneor Ethylene-Oxide CH2—CH2 O 1,3-Epoxy-Propane = Oxetane andTri-Methylene-Oxide = 1,3-Methylene- Oxide CH₂—(CH₂)—CH₂ O Epoxy-PropaneCH2—(CH2)—CH2 O Acetylene, C₂H₂ Diacetylene = 1,3-Butadiyne1,3-Butadiene CH₂═CH—CH═CH₂, less exotic high energy fuelsDi-Ethyl-Ether or surgical ether Acetone = Di-Methyl-Ketone less exotic,volatile fuels Cyclo-Propane Cyclo-Butane Hydrocarbons such as methane,propane, butane, pentane, etc. other storable fuels Methyl FormateHCOO—C₂H₅ Formamide HCO—NH₂ N,N,-Di-Methyl-Formamide HCO—N—(CH₃)₂Ethylene-Diamine H₂N—CH₂—CH₂—NH₂ Ethylene-Glycol 1,4-Dioxane =bimolecular cyclic ether of Ethylene-Glycol Paraldehyde (CH₃CHO)₃ cyclictrimer of Acetaldehyde powerful oxidizer Tetra-Nitro-Methane, C(NO₂)₄ .. . does not spontaneously decompose . . . just pass the two separatevapors over the reaction surface of the cell in the gas phase HydrogenPeroxide H2O2 low initiation energy mixtures Cyclo-Propane with Oxygen =surgical anesthetic, microjoules initiator Hypergolics UDMH =Unsymmetrical DiMethyl Hydrazine = 1,1-DiMethyl Hydrazine (CH₃)₂NNH₂UDMH is hypergolic usually with N₂O_(4 and) is a very potent carcinogenMMH MonoMethyl Hydrazine (CH₃)HNNH₂ hypergolic with any oxidizers, e.g.N₂O₄ Corrosive Toxic energetic monopropellant Hydrazine = H₂NNH₂decomposed easily with a catalyst (usually Pt or Pd or Molybdenum OxideHydrazine Hydrate

A method and system for ballistic charge carrier refraction have beendisclosed. Although the present methods and systems have been describedwith respect to specific examples and subsystems, it will be apparent tothose of ordinary skill in the art that it is not limited to thesespecific examples or subsystems but extends to other embodiments aswell.

We claim:
 1. An apparatus, comprising: one or more solid-state electricgenerators, the solid-state electric generators including at least onechemically energized solid-state electric generator; wherein the one ormore solid-state electric generators include: a solid-state junctioncomprised of a first material and a second material, wherein the firstmaterial comprises a nanoscopic cluster and is over the second materialbut maintains sufficient contact with the second material, the secondmaterial being porous, to form a solid-state electric generator; and aheat sink that removes heat from the one or more solid state electricgenerators, the heat sink having a heat sink temperature higher than anambient temperature; wherein the one or more solid-state electricgenerators use an interaction of chemically energized reactants toenergize a charge carrier between the first and second material.
 2. Theapparatus of claim 1, wherein the second material contains microscale ornanoscale protrusions at the surface.
 3. The apparatus of claim 1,wherein the at least one chemically energized solid-state electricgenerators include an electrical potential barrier that retardstransport of the charge carrier between the first material and thesecond material.
 4. The apparatus of claim 1, wherein the secondmaterial is chosen from a materials group including crystalline,polycrystalline, or porous TiO₂, SrTiO₃, BaTiO₃, Sr_x-Ba_y-Ti_z, boroncarbide, LiNiO, and LaSrVO₃ PTCDA, or3,4,9,10-perylenetetracarboxylicacid-dianhydride.
 5. The apparatus ofclaim 1, wherein the heat sink is directly connected to the secondmaterial.
 6. The apparatus of claim 1, wherein the one or moresolid-state electric generators comprise a plurality of solid-stateelectric generators that are connected electrically in series,electrically in parallel, or combinations of series and parallel.
 7. Theapparatus of claim 1, wherein the one or more solid-state electricgenerators comprise a plurality of solid-state electric generators thatare connected thermally in series, thermally in parallel, orcombinations of series and parallel.
 8. The apparatus of claim 1,comprising buss bars on the active surface of one or more solid-stateelectric generators.
 9. The apparatus of claim 1, wherein the nanoscopiccluster has discontinuous porous coverage over the second material. 10.The apparatus of claim 1, wherein the first material comprises aplurality of nanoscopic clusters.
 11. The apparatus of claim 1, whereinthe nanoscopic cluster comprises a catalyst.
 12. A chemically energizedsolid-state electric generator comprising: a solid state junctioncomprising a first material and a second material, wherein the firstmaterial comprises a nanoscopic cluster and is over the second materialbut maintains sufficient contact with the second material, the secondmaterial being porous, to form a solid-state electric generator; and aheat sink that removes heat from the one or more solid state electricgenerators, the heat sink having a heat sink temperature higher than anambient temperature; wherein an interaction of chemically energizedreactants energizes a charge carrier between the first material andsecond material.
 13. The chemically energized solid-state electricgenerator of claim 12, wherein the solid-state junction comprises aconductor-dielectric junction.
 14. The chemically energized solid-stateelectric generator of claim 12, wherein the solid-state junctioncomprises a dielectric-dielectric junction.
 15. The chemically energizedsolid-state electric generator of claim 12, wherein the solid-statejunction comprises a dielectric-conductor-dielectric junction.
 16. Thechemically energized solid-state electric generator of claim 12, whereinthe solid-state junction comprises a Schottky barrier.
 17. Thechemically energized solid-state electric generator of claim 12, whereinthe solid-state junction comprises a p-n junction potential barrier. 18.The chemically energized solid-state electric generator of claim 12,wherein the nanoscopic cluster has discontinuous porous coverage overthe second material.
 19. The chemically energized solid-state electricgenerator of claim 12, wherein the first material comprises a pluralityof nanoscopic clusters.
 20. The chemically energized solid-stateelectric generator of claim 12, wherein the nanoscopic cluster comprisesa catalyst.
 21. The apparatus of claim 1, wherein the first material hasa width that is less than the mean free path for hot carriers in thefirst material.
 22. The apparatus of claim 1, wherein the first materialhas a width that allows the carrier transit time to be shorter than theperiod of the highest lattice vibration of the first material.
 23. Theapparatus of claim 12, wherein the first material has a width that isless than the mean free path for hot carriers in the first material. 24.The apparatus of claim 12, wherein the first material has a width thatallows the carrier transit time to be shorter than the period of thehighest lattice vibration of the first material.